RF-PROPERTIES-OPTIMIZED COMPOSITIONS OF (RE) Ba2Cu3O7-   THIN FILM SUPERCONDUCTORS

ABSTRACT

The films of this invention are high temperature superconducting (HTS) thin films specifically optimized for microwave and RF applications. In particular, this invention focuses on compositions with a significant deviation from the 1:2:3 stoichiometry in order to create the films optimized for microwave/RF applications. The RF/microwave HTS applications require the HTS thin films to have superior microwave properties, specifically low surface resistance, R s , and highly linear surface reactance, X s , i.e. high J IMD . As such, the invention is characterized in terms of its physical composition, surface morphology, superconducting properties, and performance characteristics of microwave circuits made from these films.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a Continuation of U.S. patent application Ser. No.12/974,771, filed Dec. 21, 2010, which is a Continuation of U.S. patentapplication Ser. No. 11/317,889, filed Dec. 22, 2005, now U.S. Pat. No.7,867,950, which claims priority to U.S. Provisional Patent ApplicationNo. 60/639,043, filed Dec. 23, 2004, the contents of which are allincorporated by reference herein in their entirety as if fully set forthherein.

FIELD OF THE INVENTION

This invention relates to thin films of high temperature superconductingcompositions optimized for RF applications and a method formanufacturing them, more specifically rare earth compositions of(RE)Ba₂Cu₃O_(7-δ) deviating significantly from the 1:2:3 stoichiometry.

BACKGROUND OF THE INVENTION

Rare earth oxide superconductors and their ability to superconduct atsignificantly higher temperatures than previously recorded was firstreported by J. G. Bednorz and R. A. Muller in 1986 in regard to mixturesof lanthanum, barium, copper and oxygen in an article entitled “PossibleHigh T_(c) Superconductivity in the Ba—La—Cu—O system.” (64 Z. Phys.B.—Condensed Matter, pp 189-193 (1986)). Bednorz and Muller describedBa—La—Cu—O compositions that offered a substantial increase in thecritical temperature at which the material becomes superconducting overwhat had been previously known for other classes of materials. Here, thecomposition was La_(5-x)Ba_(x)Cu₅O_(5(3-y)) where x=0.75-1, y>0, and theabrupt change in resistivity occurred in the 30 Kelvin range.

This contribution led to intensive investigation in order to developmaterials having even higher transition temperatures, preferably above77 Kelvin as this enabled the use of liquid nitrogen to cool thesuperconducting equipment. In 1987, C. W. Chu and co-workers at theUniversity of Houston found that the onset T_(c) of the La—Ba—Cu—Ocompound could by increased to over 50 K by the application of pressure.(Phys. Rev. Lett. 58. 405 (1987); Science 235, 567 (1987)).

Chu and coworkers at Houston and at the University of Alabamasubsequently discovered a mixed-phase Y—Ba—Cu—O system onset havingT_(c) values near 90 K and a zero-resistance state at ˜70 K. Thiscompound had the nominal composition Y₁₋₂Ba_(0.8)CuO_(4-δ). (Phys. Rev.Lett. 58, 908 (1987). Chu and coworkers as well as scientists at AT&Tand IBM later showed this compound to consist of two phases of nominalcomposition Y₂BaCuO₅ (the “green” phase) and YBa₂Cu₃O_(6+x) (the “black”phase). The latter phase was determined to be the superconducting phase,whereas the former was semiconducting (Cava et al., Phys. Rev. Lett. 58,1676 (1987); Hazen et al., Phys. Rev. B 35, 7238 (1987); Grant et al.,Phys. Rev. Lett. 35, 7242 (1987).

Superconductivity near 90 K was also reported in a mixed-phaseLu—Ba—Cu—O compound by Moodenbaugh and coworkers (Phys. Rev. Lett. 58,1885 (1987). Chu et al. also identified superconductivity above 90 K forcompounds of the formula ABa₂Cu₃O_(6+x), where A=Y, La, Nd, Sm, Eu, Gd,Ho, Er, or Lu (Phys. Rev. Lett. 58, 1891 (1987).

The data from these differing Rare Earth (RE)BCO (RE=rare earth, B=Ba,C=Cu) compounds demonstrated that for this class of compounds, thesuperconductivity is associated with the CuO₂—Ba—CuO₂—Ba—CuO₂ planeassembly which can be disrupted by the A cations only along the c-axis.

Following this discovery, research was focused on the YBCO class ofcompounds with high temperature superconducting (HTS) properties. B.Batlogg first discovered and isolated the single crystallographic phaseresponsible for the superconducting properties of the YBCO compound. (B.Batlogg, U.S. Pat. No. 6,635,603). In isolating this single perovskitephase of a composition, Batlogg admonished that the composition wasessential to isolation of the phase and that it must be within 10% ofthe M₂M′Cu₃O_(7-δ) composition where M is a divalent cation preferablybarium and M′ is a trivalent cation preferably yttrium.

Other studies have investigated both the effects of substitution ofvarious rare earth elements for yttrium and of varying the 1:2:3 ratioof Y:Ba:Cu on the superconducting properties of HTS compositions.Multiple studies have shown the ability to partially or completelysubstitute rare earth elements except Pr, Ce and Tb and maintain a T_(c)of approximately 90 K for the resulting (RE)BCO composition. (S. Jin,Physica C 173, pp 75-79 (1991)). Additionally, further studies show thatthe c-axis coherence length and the T_(c) value increase with increasingionic radius of the rare earth element substituted for yttrium (G. V. M.Williams, Physica C 258, pp 41-46 (1996)).

Building on these discoveries, P. Chaudhari and his co-workers at IBMdeveloped a method for making thin films of high temperaturesuperconducting oxides with a nominal composition of (RE)(AE)₂Cu₃O_(9-y)where RE is a rare earth element, AE is an alkaline earth element and yis sufficient to satisfy valence demands. (Chaudhari, U.S. Pat. No.5,863,869 (1999)). The rare earth elements used included Y, Sc and La,and AE could also be substituted for by Ba, Ca or Sr. Copper was thepreferred transition metal for the oxide due to its high superconductingonset temperature and the smooth, uniform properties of the copper oxidefilms. Using this growth process, Chaudhari was able to obtain YBCOfilms with superconducting onset temperatures of about 97 Kelvin thatexhibited superconducting behavior from 50 Kelvin to in excess of 77Kelvin. These films were within 15% of the targeted (RE)(AE)₂Cu₃O_(9-y)composition, and Chaudhari noted that the exact composition was notnecessary in order to observe high temperature superconductivity.

However, in another study of (RE)BCO cation exchange in thin films, J.MacManus-Driscoll et al. noted that T_(c) decreased dramatically foroff-composition films with substitutions of rare earth (RE) elements onthe Ba site such as RE(Ba_(2-x)RE_(x))Cu₃O_(y) where RE=Er or Dy andx>0.1 (14% deviation) and where RE=Ho and x>0 (any deviation). (J. L.MacManus-Driscoll, Physica C 232, pp 288-308 (1994). J.MacManus-Driscoll further reported that the oxygen pressure at which thethin films were grown seemed to have an effect on the structuraldisordering of the RE and Ba cations as did the rare earth ion size.Small rare earth cations substituting for the larger Ba cations wouldproduce large strains on the lattice and therefore an unstable phasewhich would not likely occur.

Another study of varying the 1:2:3 stoichiometry of YBCO thin filmsnoted that large excesses of yttrium formed ultra small yttriumprecipitates leading to increased surface resistance (R_(s)) and poormicrowave quality but that a slightly enhanced copper and yttriumcontent lead to minimum surface resistance (E. Waffenschmidt, J. Appl.Phys. 77 (1) pg 438-440). Furthermore, N. G. Chew et al. analyzed theeffect of slight changes in composition on YBCO thin film structural andelectrical properties and discovered that films grown with astoichiometry close to 1:2:3 or with excess yttrium are smooth whilefilms with excess barium exhibited surface roughness and growth ofa-axis-oriented grains. (N. Chew, Appl. Phys. Lett. 57 (19) pp 2016-2018(1990). These authors further found that there is a well defined YBCOcomposition where T_(c) and J_(c) are maximized and the c-axis latticeconstant, (007) x-ray peak width, and surface roughness are minimized.These quantities were optimized for a Ba/Y ratio of 2.22±0.05(subsequently suggested to instead be equal to 2) and a Cu/(Y+Ba+Cu)ratio of 0.5. Slight changes in cation ratios away from this optimizedcomposition caused significant degradation in the parameters listedabove.

W. Prusseit et al, have created an iso-structural Dy-BCO thin filmmaterial with improved properties compared to their YBCO films. Bysubstituting dysprosium for yttrium and growing under identicalconditions as YBCO, Prusseit created films that deviated only slightlyfrom the 1:2:3 stoichiometry. Compared to their YBCO films, thesematerials exhibited better chemical stability and enhanced transitiontemperatures (by 2-3 K), and they also had a 20% reduction in surfaceresistance (R_(s)) at 77 K: ˜250 μΩ vs. ˜300 μΩ at 10 GHz, measured in amicrowave cavity (W. Prusseit, Physica C 392-396, pp 1225-1228 (2003)).Hein (High-Temperature Superconductor Thin Films at MicrowaveFrequencies (Springer Tracts in Modern Physics, 155), Berlin, 1999) andothers have measured somewhat lower surface resistance. ˜200 μΩ at 10GHz and 77 K, in cavity measurements of YBCO thin films.

The compositions of these (RE)BCO compounds may be altered substantiallyfrom the nominal 1:2:3 stoichiometry in order to optimize theirproperties for specific applications. It is the primary object of thisinvention to provide high temperature superconducting thin films thathave the lowest possible RF surface resistance (R_(s)) values as well asthe lowest achievable RF nonlinearities. This often requires fabricationof (RE)BCO films that deviate significantly from the 1:2:3 composition.It is another object of this invention to provide a thin filmsuperconductor that is optimized for RF/microwave applications. It isanother object of this invention that the film has a low surfaceresistance. It is another object of this invention that the film has ahighly linear RF/microwave surface reactance. It is another object ofthis invention that the stoichiometry of the film deviates by at least10% from the standard 1:2:3 stoichiometry and with full substitution foryttrium by a rare earth element.

SUMMARY OF THE INVENTION

The films of this invention are high temperature superconducting (HTS)thin films specifically optimized for microwave and RF applications. Theprior art (RE)BCO films exhibiting high temperature superconductingproperties were nominally of the composition (RE)_(x)Ba_(y)Cu₃O_(7-δ)where RE=a rare earth element, preferably yttrium, x=1, y=2 and 0≦δ≦1.This 1:2:3 stoichiometry has since been the focus of much studyincluding varying the rare earth element, full and partial substitutionsfor RE, for Ba, and for Cu, oxygen doping, and deviations from the 1:2:3stoichiometry.

The present invention focuses on RE HTS films specifically optimized formicrowave and RF applications. The RF/microwave HTS applications requirethe HTS thin films to have superior microwave properties, specificallylow surface resistance, R_(s), and highly linear surface reactance,X_(s), i.e. high J_(IMD). As such, the invention is characterized interms of its physical composition, surface morphology, superconductingproperties, and performance characteristics of microwave circuits madefrom these films

In particular, this invention focuses on compositions having asignificant deviation from the 1:2:3 stoichiometry in order to createthe films optimized for microwave/RF applications. These films have aRE:Ba ratio of less than 1.8, which deviates more than 10% from thetypical ratio of 2, and preferably less than 1.7. The research has shownthat the highest quality factor values, Q, representing the surfaceresistance of patterned films, peak at a particular Ba:RE ratio for eachRE and that these ratios deviate significantly from the 1:2:3stoichiometry.

Additionally, the performance characteristics of the HTS films naturallyaffect their efficacy in RF/microwave HTS applications. Specificallydesirable are low surface resistance, R_(s), (<15 micro-ohms at 1.85 GHzand 77 K) and highly linear surface reactance, X_(s), i.e., high J_(IMD)values (>10⁷ A/cm², preferably >5×10⁷ A/cm² at 77 K). HTS thin filmswith such properties permit the fabrication of extremely selectivefilters (60-dB rejection within 0.2% relative frequency, to 100-dBrejection within 0.02% relative frequency, with extremely low in-bandinsertion loss (<1-dB, preferably <0.2-dB) in an extremely small size(<10-cm² filter chips), which can handle the interference power levelsexperienced at the front end of a cellular telephone base stationreceiver (−50 dBm to −28 dBm, to as high as −12 dBm to 0 dBm or possiblyeven higher) without producing undesirable distortion in the passband,particularly intermodulation distortion, and more particularlyintermodulation distortion products comparable to background noiselevels (−173.8 dBm/Hz). Thus, the films of this invention are alsocharacterized by their optimized microwave and RF properties. These andother objects, features and advantages will be apparent from thefollowing more particular description of the preferred embodiments.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows θ-2θ x-ray diffraction scans for several (RE)BCO thin filmsgrown on MgO substrates.

FIG. 2 displays the 2θ (005) x-ray peak positions as a function of theBa/RE ratio for different compositions of the various (RE)BCO thin filmsindicated.

FIG. 3 displays the 2θ(005) x-ray peak intensities as a function of theBa/RE ratio for different compositions of the various (RE)BCO thin filmsindicated.

FIG. 4 shows representative x-ray diffraction φ-scans of the (103) peakfor several (RE)BCO films, including Er-, Ho-, and Dy-BCO (left panels).The right panel plots display the χ-scans for (RE)BCO films taken aboutthe (104) peak.

FIG. 5 shows a higher sensitivity φ-scan of the (103) Bragg angle for aDy-BCO thin film.

FIG. 6 shows an atomic force microscope (AFM) scan of the surface of aDy-BCO thin film that is optimized for RF properties.

FIG. 7 shows an AFM scan of the surface of a Ho-BCO thin film that isoptimized for RF properties.

FIG. 8 shows an AFM scan of the surface of a Er-BCO thin film that isoptimized for RF properties.

FIG. 9 shows an AFM scan of the surface of a Nd-BCO thin film that isoptimized for RF properties.

FIG. 10 displays the room-temperature (300 K) dc resistivity values as afunction of the Ba/RE ratio for different compositions of the various(RE)BCO thin films indicated.

FIG. 11 shows the de resistivity as a function of temperature, ρ(T), fora Dy-BCO film optimized for RF properties. A detail of thesuperconducting transition is shown in the inset.

FIG. 12 shows the ρ(T) curve for a Ho-BCO film optimized for RFproperties. A detail of the superconducting transition is shown in theinset.

FIG. 13 shows the ρ(T) curve for a Er-BCO film optimized for RFproperties. A detail of the superconducting transition is shown in theinset.

FIG. 14 shows the ρ(T) curve for a Nd-BCO film optimized for RFproperties. A detail of the superconducting transition is shown in theinset.

FIG. 15 displays the zero-resistance T_(c) values as a function of theBa/RE ratio for different compositions of the various (RE)BCO thin filmsindicated.

FIG. 16 shows the geometry of the quasi-lumped element resonator designused to measure the Q values of our (RE)BCO films. This resonator has acenter frequency of about 1.85 GHz for films on MgO substrates. Theresonator dimensions are 5.08-mm square.

FIG. 17 displays the unloaded quality factor (Q_(u)) as a function ofthe Ba/RE ratio for different compositions of the various (RE)BCO thinfilms indicated. These Q_(u) values were measured at a temperature of 67K and input power of −10 dBm for lumped-element RF resonators having acenter frequency of about 1.85 GHz. The dotted line at Ba/RE=2represents the on-stoichiometric value of the 1:2:3 compound.

FIG. 18 displays the Q_(u) values as a function of the RE/Cu ratio fordifferent compositions of the various (RE)BCO thin films indicated.These Q_(u) values were measured at a temperature of 67 K and inputpower of −10 dBm for lumped-element RF resonators having a centerfrequency of about 1.85 GHz. The dotted line at RE/Cu=1/3 represents theon-stoichiometric value of the 1:2:3 compound.

FIG. 19 displays the Q_(u) values as a function of the Ba/Cu ratio fordifferent compositions of the various (RE)BCO thin films indicated.These Q_(u) values were measured at a temperature of 67 K and inputpower of −10 dBm for lumped-element RF resonators having a centerfrequency of about 1.85 GHz. The dotted line at Ba/Cu=2/3 represents theon-stoichiometric value of the 1:2:3 compound.

FIG. 20 shows the layout of the 10-pole B-band cellular filter designused for our IMD tests. The filter dimensions are 18-mm by 34-mm.

FIG. 21 shows a block diagram for an intermodulation distortionmeasurement of an HTS filter.

FIG. 22 shows the typical S₁₁ response of a 10-pole B-band cellular RFfilter fabricated from a (RE)BCO thin film. The positions of the inputfrequencies for three two-tone intermodulation distortion testmeasurements are shown.

FIG. 23 shows the results of intermodulation distortion (IMD) testmeasurements made at 79.5 K as a function of the Ba/Dy ratio for several10-pole B-band filters patterned from Dy-BCO films. The dotted linesindicate the required specification levels.

FIG. 24 shows the results of IMD test measurements made at 79.5 K as afunction of the Ba/Ho ratio for several 10-pole B-band filters patternedfrom Ho-BCO films. The dotted lines indicate the required specificationlevels.

FIG. 25 shows the results of IMD test measurements made at 79.5 K as afunction of the Ba/Er ratio for several 10-pole B-band filters patternedfrom Er-BCO films. The dotted lines indicate the required specificationlevels.

FIG. 26 shows the results of IMD test measurements made at 79.5 K forfour 10-pole B-band filters patterned from Nd-BCO films. The dottedlines indicate the required specification levels.

FIG. 27 displays the unloaded quality factor (Q_(u)) as a function ofthe Ba/Dy ratio for different compositions of the various Dy-BCO thinfilms indicated. These Q_(u) values were measured at a temperature of 67K and input power of −10 dBm for lumped-element RF resonators having acenter frequency of about 1.85 GHz. The solid line at Ba/Dy=2 representsthe on-stoichiometric value of the 1:2:3 compound.

FIG. 28 displays the unloaded quality factor (Q_(u)) as a function ofthe Ba/Dy ratio for different compositions of the various Dy-BCO thinfilms indicated. These Q_(u) values were measured at a temperature of 77K and input power of −10 dBm for lumped-element RF resonators having acenter frequency of about 1.85 GHz. The solid line at Ba/Dy=2 representsthe on-stoichiometric value of the 1:2:3 compound.

FIG. 29 displays the ratio of high input power (+10 dBm) to low inputpower (−10 dBm) Q factors for different compositions of the variousDy-BCO thin films indicated wherein the Q_(u) values were measured at atemperature of 67 K.

FIG. 30 displays the ratio of high power to low power Q factors fordifferent compositions of the various Dy-BCO thin films indicatedwherein the Q_(u) values were measured at a temperature of 77 K.

FIG. 31 displays the 2θ(005) x-ray peak intensities as a function of theBa/Dy ratio for different compositions of Dy-BCO thin films.

FIG. 32 displays the room-temperature (300 K) de resistivity values as afunction of the Ba/Dy ratio for different compositions of Dy-BCO thinfilms.

FIG. 33 displays the zero-resistance T_(c) values as a function of theBa/Dy ratio for different compositions of Dy-BCO thin films.

Table I displays the maximum Q_(u) values at ˜1.85 GHz obtained forseveral of our (RE)BCO thin films measured using a patterned testresonator. The measurements were made at 67 K and 77 K for an inputpower of −10 dBm. This table also shows the R_(s) values that we havecalculated from these Q_(u) values.

TABLE 1 Unloaded Q values of our highest-Q films measured with ourstandard test resonator at −10 dBm input power. The R_(s) values arecalculated from these measured Q values. These calculated R_(s) valuesof the patterned structures are less than the actual measured R_(s)values of the bulk films. T = 67K T = 77K Material Unloaded Q R_(s) (μΩ)f₀ (MHz) Unloaded Q R_(s) (μΩ) f₀ (MHz) YBCO 83599 4.9 1847.94 50470 8.11848.23 Dy-BCO 52200 7.8 1851.13 37000 11.1 1850.29 Ho-BCO 70500 5.81850.07 39000 10.5 1849.95 Er-BCO 45300 9.0 1840.60 18800 21.8 1838.60Nd-BCO 80866 5.1 1847.09 59341 6.9 1848.14

DETAILED DESCRIPTION OF THE INVENTION

As previously mentioned, this invention relates to high temperaturesuperconducting (HTS) thin films with compositions that are optimizedfor RF/microwave applications and methods for reliably producing suchfilms. As such, the invention is characterized in terms of its physicalcomposition, surface morphology, superconducting properties, andperformance characteristics of microwave circuits made from these films(filters, delay lines, couplers, etc.; particularly bandpass andbandreject filters, more particularly bandpass and bandrejectpreselector filters for cellular telephone base station receivers). Thedistinction between HTS (RE)BCO films of the prior art and the (RE)BCOfilms of this invention is found both in the composition that deviatessignificantly from the 1:2:3 stoichiometry and the highly optimized RFproperties of the new composition.

DEFINITIONS

For our purposes, a thin film may be defined as a layer (generally, verythin) of a material that is grown, deposited, or otherwise applied to asuitable supporting substrate. The thickness of this film may range fromabout one nm (10⁻⁹ m) to several microns (>10⁻⁶ m) thick. The typicalrange of thin film thickness for many applications is from 100 nm to1000 nm.

High temperature superconductors (HTS) encompass a broad class ofceramic materials, typically oxides, more typically copper oxides orcuprates, that have a transition temperature or critical temperature,T_(c), below which these materials are superconducting. Above thiscritical temperature, they generally behave as metallic, or “normal,”conducting materials. HTS materials are further generally characterizedas having T_(c) values above about 30 K. Examples of HTS materialsinclude La₂CaCu₂O₆, Bi₂Sr₂CaCu₂O₈, YBa₂Cu₃O₇, Tl₂Ba₂CaCu₂O₈,HgBa₂CaCu₂O₇, etc. These materials must have a well-defined crystalstructure in order to be superconducting, i.e., they must have a veryspecific regular and repeated arrangement of their constituent atoms.

The rare earth (RE) elements are the 15 lanthanide elements with atomicnumbers 57 through 71 that are in Group IIIA of the Periodic Table:lanthanum, cerium, praseodymium, neodymium, promethium, samarium,europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium,ytterbium, and lutetium. Yttrium (atomic number 39), a Group IIIAtransition metal, although not a lanthanide is generally included withthe REs as it occurs with them in natural minerals and has similarchemical properties. Commonly included with the REs because of theirsimilar properties are scandium (atomic number 21), also a Group IIIAtransition metal, and thorium (atomic number 90), an element in theactinide series of the Periodic Table.

Composition

The most ubiquitous HTS material is YBCO, which consists of an orderedamount and arrangement of Y, Ba, Cu, and O atoms. The fundamentalrepeated unit of this material's specific atomic arrangement is known asthe unit cell, consisting nominally of one Y, two Ba, three Cu, andseven O atoms. The size of this compound's orthorhombic unit cell isabout 3.82×3.89×11.68 Angstroms in the a-, b-, and c-axis directions,respectively. The atomic ratios needed to form this compound aredescribed by the chemical formula YBa₂Cu₃O_(7-δ), where the oxygencontent is variable between 6 and 7 atoms per unit cell, or 0≦δ≦1. Forsingle-phase materials with this composition and having high crystallinequality and purity, the T_(c) value is determined largely by the valueof δ. YBCO is a superconductor for δ<˜0.6, with values of δ near 0 beinggenerally preferred in order to provide the highest T_(c) values.

YBCO is the most widely studied HTS material, and much is known abouthow to make it in single phase form, i.e., consisting of solely thecomposition mentioned above and containing no other phases. However,many other similar compounds can also be fabricated that may havesimilar or superior superconducting properties, depending on theapplication. These compounds may have Y:Ba:Cu ratios that are differentfrom 1:2:3, and they may also consist of elements other than Y or Ba. Ageneralized nomenclature for the makeup of this compound may thus bewritten as M′_(x)M_(y)Cu₃O_(7-δ), where M′ may in general be anyessentially trivalent ion or combination of ions, and M may be anyessentially divalent ion or combination of ions. The ratios of M′:Cu,M:Cu, and M′:M may also vary substantially from the nominal values of1:3, 2:3, and 1:2, respectively. While the full range of parameter spacehas not been explored, it is reasonable to believe that compounds withcation ratios deviating from the nominal by as much as 50% may still besuperconductors, e.g. 1:6<M′:Cu<1:2, 1:3<M:Cu<1:1, and 1:4<M′:M<3:4.However, significantly altering the composition from the 1:2:3stoichiometry does affect the specific properties of the compositionincluding critical current density (J_(c)), normal-state resistivity(ρ), critical temperature (T_(c)), and surface resistance (R_(s)).

In order to provide high T_(c) values, Ba is generally preferred as thedivalent element, or M in the above formula. Full or partialsubstitutions of many elements for Ba tend to decrease T_(c) or destroysuperconductivity altogether. These elements include Sr, La, Pr and Eu.(Y. Xu, Physica C 341-348, pp 613-4 (2000) and X. S. Wu, Physica C 315,pp 215-222 (1999). Similarly, the Cu atoms may be doped with Co, Zn, Ni,etc., the effect of most of which is to decrease T_(c), though theabsolute effect (e.g., charge transfer or disruption ofsuperconductivity on the Cu—O planes) depends on whether the Cu(1) orCu(2) sites are affected. (Y. Xu, Phys. Rev. B Vol 53, No. 22, pp15245-15253 (1996). Some partial substitutions on the Y sites may have asimilar effect, such as Ca, Ce, and Pr (L. Tung, Phys. Rev. B Vol 59,No. 6, pp 4504-4512 (1999) and C. R. Fincher, Phys. Rev. Lett. 67 (20)pp 2902-2905 (1991)). However, there are many known partial or completesubstitutions for Y that lead to similarly high or greater T_(c) valuesthan YBCO. Many of these known substitutions come from the rare earthfamily of elements. In general, rare earth elements that have a largerionic radius produce higher T_(c) values for these (RE)BCO compounds (G.V. M. Williams, Physica C 258, pp 41-46 (1996)).

While it is key to maintain the defining property of superconductivityacross the range of compositions available for these related compounds,our research has shown that the compositions may be alteredsubstantially from the nominal 1:2:3 stoichiometry in order to tailortheir properties for specific applications. For example, compositionsnear 1:2:3 may be preferred for multilayer or active device applicationsfor which smooth thin film surfaces are of paramount importance.Conversely, optimization of HTS films for RF applications requires theproduction of thin films that strike a balance between having the lowestpossible RF surface resistance (R) values and the lowest RFnonlinearities that are achievable. This in turn often requires thefabrication of (RE)BCO films that deviate significantly from the 1:2:3composition.

The HTS thin films of this invention are optimized for RF applications,and as such they have the lowest possible RF surface resistance (R_(s))values and the lowest possible RF nonlinearities. In order to achievethis optimization, the film compositions have the nominal formula(RE)_(x)Ba_(y)Cu₃O_(7-δ), where RE is one of the previously defined rareearth elements, preferably Dy, and where the ratio y:x is preferablybetween about 1.5-1.8, more preferably between about 1.55-1.75, and mostpreferably between about 1.6-1.7.

Substrates

The superconducting properties of HTS materials are extremely sensitiveto their degree of crystalline perfection. This places severeconstraints on the choice of a suitable substrate material on whichhigh-quality HTS films may be grown. Some of these constraints includecrystal structure, compatibility with the growth process, chemicalcompatibility, compatibility with the application, as well as otherrequirements imposed by nature.

Perhaps the most important requirement is the crystal structure. Thesubstrate must have an appropriate lattice match with the HTS film suchthat epitaxial growth of the film can occur and a well-oriented filmwill form. A poor lattice match can lead to dislocations, defects, andmisoriented grains in the film. In general, the substrate should beavailable in single-crystal form in order to meet these requirements.

The substrate must be able to withstand the high processing temperaturesduring the growth process that are required for the crystallization ofthe HTS compound. In addition, structural integrity and a reasonablethermal expansion match with the HTS film is required in order toprevent strain and cracking of the film during the cool down cycle fromthe growth temperature or from any other subsequent thermal cyclings.

The substrate must be chemically compatible with (RE)BCO, non-reactive,and with minimal diffusion into the film at high temperature.

The substrate must be available in a size large enough for the intendeduse of the HTS thin film. For example, certain passive microwavecircuits or high-volume electronics applications require a largesubstrate size. A minimum substrate of 2″ in diameter is typical forthese applications, though larger sizes are often desirable ifavailable. The substrate may also be required to have physicalproperties that are compatible with experimental measurement techniquesor applications. For most applications the substrates should be stable,mechanically robust insulators. Other requirements may includetransparency in the infrared for optical transmission measurements,constituent elements or structure that do not interfere withspectroscopic measurements such as Rutherford backscattering (RBS) orenergy-dispersive x-ray analysis (EDX), and a low dielectric constantand loss tangent for microwave measurements and applications at theintended temperature of operation.

A handful of single-crystal substrates meet some or all of theserequirements. Examples include MgO, Al₂O₃, LaAlO₃, NdGaO₃,(La_(0.18)Sr_(0.82))(Al_(0.59)Ta_(0.41))O₃, and SrTiO₃. The last fourhave an excellent lattice match to (RE)BCO. The high dielectric constantand loss tangent of SrTiO₃ make it useless for microwave applications,however. LaAlO₃ and NdGaO₃ are better in this regard, though LaAlO₃suffers from the fact that it tends to twin, and these twin boundariescan be formed and become mobile at typical processing temperatures.Al₂O₃ is a low-loss substrate and is widely available in severaldifferent orientations and sizes. However, it reacts strongly with(RE)BCO at high temperatures, requiring the use of an appropriate bufferlayer. In addition, Al₂O₃ has a poor thermal expansion match to (RE)BCO,causing a tendency for the films to crack upon cooldown. MgO hasrelatively low loss and a good thermal expansion match to (RE)BCO,making it a good choice for RF applications. However, MgO has a muchlarger lattice mismatch than the other examples listed above, so thatgreat care must be taken to insure that the (RE)BCO films grown on MgOare well oriented. In particular, it is relatively common for (RE)BCOfilms grown on MgO to contain in-plane-rotated grains and 45° grainboundaries. (B. H. Moeckly, Appl. Phys. Lett. 57, 1687-89 (1990). Theminimization of the amount of these high-angle grain boundaries ismandatory for good microwave performance, particularly for high RFlinearity. Certain MgO substrate surface treatments may be instituted tohelp control the number of high-angle grain boundaries, but greatereffort is required to further suppress formation of these grainboundaries, particularly for demanding RF applications. The growthmethod, growth conditions, and particularly the composition of the(RE)BCO films must all be chosen and adjusted to minimize the amount of45° grains in films grown on MgO.

Film Morphology and Microstructure

The anisotropic transport properties of (RE)BCO, its orthorhombiccrystal structure, and its small superconductive coherence length meanthat the (RE)BCO films must have excellent crystalline structure andorientation. This is particularly true in order to obtain good microwaveproperties. Hence, the films must be substantially free of secondaryphases, they must possess good epitaxy both in-plane (parallel to thesubstrate surface) and out-of-plane (perpendicular to the substratesurface). Typically, the c-axis of (RE)BCO is aligned perpendicular tothe substrate surface. All the grains in the film must be so aligned,and they must be highly aligned with respect to one another. The degreeof this crystalline order is typically characterized by θ-2θ x-raydiffraction scans, where the requirements are the existence of onlyc-axis-oriented (001) spectral lines having narrow peak widths, and alsonarrow peak widths of the so-called ω-scan, or rocking curve scan abouta given Bragg angle. The θ-2θ measurement can also detect the presenceof spectral lines due to a-axis-oriented grains within the film. Thesegrains may also be detected by a χ-scan about an appropriate Braggangle.

For a thin film with good microwave properties, the amount of a-axisgrains in the film is ideally zero, so that the intensity of a-axisx-ray peaks relative to c-axis x-ray peaks for a c-axis-oriented film isideally zero, and preferably much less than 1%. In addition, thec-axis-oriented grains should also be in-plane oriented, meaning thatthey are in registry with each other and with the substrate crystalstructure. Grains that are rotated with respect to the overall in-planelattice structure lead to nonzero-degree angle grain boundaries. Thesuperconducting transport across such nonzero-angle grain boundaries, inparticular high-angle grain boundaries and 45° grain boundaries, isdegraded likely due to strain, the high oxygen mobility, and smallcoherence length of (RE)BCO (B. H. Moeckly et al., Phys. Rev. B 47, 400(1993). J_(c), R_(s), and the RF nonlinearities may all be adverselyaffected by the presence of these high-angle grain boundaries. Thepresence of these rotated grains and grain boundaries may be detected byφ-scan x-ray measurements taken about an appropriate Bragg angle.Ideally, the amount of nonaligned φ-scan peaks should be zero, andpreferably less than 0.1% of the magnitude of the aligned peaks, morepreferably less than 0.05%, and most preferably less than 0.02%.

FIG. 1 shows the θ-2θ scans for several 700-nm-thick (RE)BCO films madeby us and optimized for RF applications. In addition to YBCO, thesefilms include RE substitutions of Er (EBCO), Ho (HBCO), Dy (DBCO), andNd (NBCO). The x-ray scans display the presence of only (001) peaks,indicating that the films are single-phase and highly c-axis aligned,and that no a-axis-oriented grains exist in the films. Note that therelative peak intensities of the (RE)BCO films are different from YBCO,indicative of the effect of the different RE ionic radii. FIG. 2 showsthe (005) peak positions vs. the Ba/RE ratio for several (RE)BCO filmswith different compositions, indicating slightly different c-axislattice parameters for these films. FIG. 3 shows the intensities of the(005) peaks for these films. FIG. 31 shows the intensities of the (005)peaks for DBCO films of varying compositions as a function of the Ba/Dyratio. These DBCO films are inclusive of those shown in FIG. 3, but arenot necessarily optimized for RF properties. Here, it is observed thathigh peak intensities, indicative of good crystallinity, are obtainedfor DBCO film compositions that deviate significantly from theon-stoichiometric ratio indicated by the solid line on the graph. FIG. 4shows representative φ-scans of the (103) peak for several (RE)BCO films(left hand panels). Note that any peaks at 45° are absent, indicating anabsence of 45° oriented grains and grain boundaries. FIG. 5 shows ahigher sensitivity φ-scan for one of our Dy-BCO films. The y-axis isplotted on a log scale, and it can be seen that only very weak peaksoccur at 45° relative to the main peak. This scan indicates the degreeto which this film is free from high-angle grain boundaries. Theintensity of the weak lines at 45° is only about 0.012% of the maximumcentral peak indicating that almost none of the grains are misaligned.This is important for optimization of the RF properties of these films,most notably their RF nonlinearities. The right-hand panel of FIG. 4displays the χ-scans for (RE)BCO films taken about the (104) peak; asindicated in FIG. 1, these scans also demonstrate the absence ofa-axis-oriented grains.

The surface morphology of (RE)BCO thin films is typically measured byscanning probe profilometry, atomic force microscopy (AFM), and scanningelectron microscopy (SEM). In general, smooth films are preferred forapplications, though some degree of surface roughness may be toleratedin deference to the optimization of other important properties such asJ_(c) and R_(s). Still, it is desirable to have an RMS surface roughnessas determined by AFM, say, which is less than ˜10 nm.

FIGS. 6-9 show typical AFM images of Dy-, Ho-, Er-, and Nd-BCO filmsover a 5 μm×5 μm area. These films have been optimized in terms of theirRF properties. The RMS surface roughness for these films is a few nm.FIG. 6 shows the surface morphology for a high-Q DBCO film with very lowRF nonlinearities. The grain size of this film can be seen to be roughly2 μm in diameter. We also observe some sub-micrometer-sized particles onthe surface of the films, seen as the bright dots in the figure. EDXanalysis indicates a high Cu signal for these particles, implying thatthey composed of Cu oxide. The grains for the HBCO film of FIG. 7 have asmaller, squarer appearance, and this film has a general absence of CuOparticulates. The optimized EBCO surface depicted in FIG. 8 has asmaller grain size still, and in this case there also exist CuOparticulates. The grains of the NBCO film of FIG. 9 are also square inappearance and have a size of less than 0.5 μm. The different surfacemorphologies for these optimized (RE)BCO films are in generalreflections of the different composition and growth conditions needed toachieve the best RF properties for the different RE substitutions.

Film Characterization Methodology

The (RE)BCO films are further characterized by measuring theircomposition and their electrical properties, including the dcresistivity (ρ) as a function of temperature [ρ(T)], T_(c) value andtransition width, critical current density (J_(c)), and RF surfaceresistance (R_(s)). The films are also subsequently patterned into RFcircuits for which we measure the unloaded quality factor (Q) values,intermodulation distortion (IMD), and nonlinear critical current density(J_(IMD)).

The composition of the films of this invention was measured usingRutherford backscattering spectrometry (RBS) and inductively coupledplasma spectroscopy (ICP). These techniques are both capable of a highdegree of accuracy and precision, though achieving a measurementaccuracy of 1σ or 2σ equal to 1% is a difficult task and requires morecare than is the norm for these techniques. In the RBS analysistechnique, fast, light ions (typically He ions or alpha particles) areaccelerated toward the sample, some of these ions are backscattered dueto Rutherford (Coulomb) scattering from atomic nuclei within the sample,and the energy spectrum of those backscattered particles is analyzed.The ion energies are typically in the range of several hundred toseveral thousand keV, and the energy of a backscattered ion depends onthe mass of the target atom with which it has collided. Thus, the energyspectrum of the backscattered ions allows identification of the elementscomprising the sample and their ratios (stoichiometry). In addition, asthe incident ions traverse the sample, they lose energy due to inelasticscattering with electrons. This energy loss occurs in a known way andtherefore allows determination of sample composition as a function ofdepth. However, for thick films, the spectral peaks of the measuredconstituent elements can overlap, requiring careful fitting of thespectra to extract the composition, and this procedure involvesuncertainty and can introduce error. Therefore, in order to obtain thehighest accuracy by simply counting the number of counts under eachpeak, sufficiently thin films must be used so that the peaks due to RE,Ba, and Cu can be completely separated. We have grown sufficiently thin(RE)BCO films for this purpose, and the results of these measurementshave shown a compositional accuracy of 2σ≦±1%. Note that thismeasurement technique is quantitative and does not require the use of acomparison standard.

In the ICP technique, the thin films are digested in an acidic solutionwhich is then introduced into a high-temperature (up to 10,000° C.)plasma discharge. The plasma ionizes and excites the constituent atomsin the solution, and as these atoms decay to a lower energy state, theyemit light of a characteristic wavelength that can be detected by ahigh-resolution spectrometer. This is the so-called ICP-AES (atomicemission or optical emission spectroscopy) technique. ICP hence permitsmeasurement of multiple elements simultaneously. ICP-AES has detectionlimits typically at the μg/L level in aqueous solutions. This techniquecan be very accurate and precise; an accuracy of 1σ<±1% is obtainablewith careful measurement. The method requires the use of a comparisonstandard. It does not have an accuracy limitation as a function of thinfilm thickness, however, as does RBS. Hence in testing our compositions,we have used RBS and ICP together. First, we have made careful RBSmeasurements on very thin films in order to determine their compositionto a high degree of accuracy. We have then confirmed that the ICPmeasurements on these same samples agree with the RBS numbers. Thisallows us to have confidence that the ICP-AES measurement of thicker(RE)BCO films shares this same degree of desired accuracy, i.e., 1σ<±1%.

The dc resistivity ρ is measured by a standard four-point-probetechnique. The room-temperature resistivity of high-quality (RE)BCOfilms is typically between 150 and 300 μΩcm, though this value varies asa function of RE element and of film composition. FIG. 10 shows theroom-temperature (300 K) resistivity values of several (RE)BCO films asa function of composition, specifically the Ba/RE ratio. FIG. 32 showsthe room-temperature resistivity values for several DBCO films as afunction of the Ba/Dy ratio. These DBCO films are inclusive of thoseshown in FIG. 10, but are not necessarily optimized for RF propertiesHere, it is observed that the room temperature resistivity valuesindicative of high quality films are obtained for DBCO film compositionsthat deviate significantly from the on-stoichiometric ratio (indicatedby the solid line on the graph), particularly within Ba/Dy ratiosranging between about 1.5-1.8, with particularly good resistivity valuesachieved for a Ba/Dy ratio of 1.76. The temperature dependence of theresistivity is shown in FIGS. 11-14 for several (RE)BCO films. Thetemperature dependence of ρ for good films is typically linear orslightly downwardly bowed indicative of so-called overdoped behavior, asthese plots indicate. The measurement of ρ(T) is also used to determineboth the width (in temperature) of the transition to the superconductingstate and the zero-resistance T_(c) value. The detail of thesuperconducting transition region of these films is shown in the insetof FIGS. 11-14. The T_(c) values for (RE)BCO films are typically between87 and 91 K (FIGS. 11-13), though the higher ionic radius REsubstitutions may have T_(c) values as high as 95 K, as shown for theNBCO film in FIG. 14. The transition from the normal state tosuperconducting state typically occurs within 0.5 K for high qualityfilms, as the figures indicate.

The T_(c) values of the (RE)BCO samples prepared by the process of thisinvention are 88.5(5), 88.9(5), 89.2(5), 89.6(5), and 94.5(8) K for Er,Y, Ho, Dy, and Nd, respectively. These values were measured immediatelyfollowing deposition. Since the films are oxygen overdoped as judged bythe slope of the R-T curves, the measured T_(c) values are slightlylower than the highest values known for these compounds. FIG. 15 plotsthe T_(c) values for different compositions of our Ho-, Er-, and Dy-BCOfilms. FIG. 33 plots the T_(c) values for different compositions ofadditional DBCO films. These DBCO films are inclusive of those shown inFIG. 15, but are not necessarily optimized for RF properties. It can beseen that high T_(c) values are obtained even for compositions deviatingsubstantially from the on-stoichiometric (1:2:3) value, indicated by thesolid vertical line.

The RF surface resistance of (RE)BCO thin films may be measured in anumber of ways, including cavity or parallel plate resonator techniquesusing bulk (unpatterned) films. R_(s) is typically measured atfrequencies between a few hundred MHz and 10 s of GHz. R_(s) may also beextracted from the Q measurements of patterned resonators of variouskinds, e.g., microstrip, quasi-lumped element, etc. Extraction of R_(s)from the measured Q values of these structures requires careful modelingof the resonator performance to determine the geometric parameter Γ_(Q).The relationship between R_(s) and Q can be written as

$R_{s} = {\omega_{0}\Gamma_{Q}\frac{1}{Q}}$

where w0 is the resonant frequency, Γ_(Q) is a parameter that dependsonly on the resonator geometry, and Q is the measured unloaded qualityfactor of the resonator. The extracted R_(s) value of patternedstructures is typically higher than the R_(s) value obtained by directmeasurement of the bulk films in an RF cavity. This may be caused bypatterning the film, which may introduce defects that can add additionalresistive RF losses in the Q measurement. It may also arise fromuncertainties in Γ_(Q) or the non-uniformity of the current density inmicrostrip resonators which is generally not present in bulk filmmeasurement systems.

Device Performance Characterization

For evaluation of the RF properties of our (RE)BCO films and fordetermining the utility of these materials for microwave filterapplications, we have fabricated microwave resonators and filters fromthese films. These passive devices require a ground plane and hencenecessitate depositing double-sided films. Quasi-lumped elementresonators were patterned using standard photolithographic processingand inert ion etching. The geometry of our test resonator is shown inFIG. 16. The materials are characterized by measuring the unloadedquality factor, Q_(u), of this standard test resonator which has acenter frequency of about 1.85 GHz at 77 K for (RE)BCO resonatorspatterned on MgO substrates. The Q_(u) was measured for a range ofcomposition and growth conditions of each (RE)BCO material, and thegrowth conditions and composition of each material were optimized toachieve maximum Q_(u). We have demonstrated Q_(u) values that aresufficient for cellular microwave applications for Dy-BCO, Er-BCO,Ho-BCO and Nd-BCO thin films. Indeed, for 700-nm-thick films, we haveachieved unloaded Q values over 40,000 at 1.85 GHz, 67 K, and −10 dBminput power for our test resonator structure using each of thesematerials. We subsequently extracted the R_(s) value of the films bymodeling the electromagnetic field distribution of the resonatorgeometry. Good R_(s) values for microwave applications are less than ˜15μΩ at 1.85 GHz and 77 K, and more preferably less than ˜10 μΩ, and mostpreferably less than about 8μΩ.

FIG. 17 shows the unloaded Q of our (RE)BCO lumped-element microwaveresonators vs. the relative Ba/RE ratio. These measurements were made at67 K and −10 dBm input power. The Q_(u) values of these films areslightly lower than our highest Qs obtained with YBCO films. The dottedline at Ba/RE=2 represents the on-stoichiometric value of the 1:2:3compound. It can be seen that the highest Q values are obtained awayfrom this ratio. Our Nd-BCO films display higher Q_(u) values at 67 K,reaching 80,000 (not shown on this plot), comparable to the highest Qsobtained with YBCO films. At 77 K, the Q values of Nd-BCO films canexceed those of YBCO. Although there is scatter in the data, the trendfor all three materials shown in FIG. 17 is similar. There exists foreach (RE)BCO film a value of the Ba:RE ratio for which the Q is maximal,and the Q values drop for ratios away from the maximum in a similar wayfor each RE element. FIG. 18 shows these Q_(u) values measured as afunction of the RE/Cu ratio, and FIG. 19 plots these data as a functionof Ba/Cu. The dotted lines indicate the on-stoichiometric ratios ofthese quantities, and it is again observed that high Q values areobtained for compositions that deviate significantly from these nominalratios. Table I displays the maximum Q_(u) values obtained for testresonators made from our (RE)BCO films measured at 67 K and 77 K for aninput power of −10 dBm. This table also shows the R_(s) values that wehave calculated from these Q_(u) values.

FIG. 27 displays additional data on the unloaded quality factor (Q_(u))as a function of the Ba/Dy ratio for different compositions of thevarious DBCO thin films indicated. These DBCO films are inclusive ofthose shown in FIG. 17, but are not necessarily optimized for RFproperties. Hence whereas FIG. 17 represents the best Q valuesobtainable at each composition, FIG. 27 shows a range of Q values ateach composition, because other properties of the films may not beoptimized, e.g., growth temperature, film thickness, surface morphology,or crystallinity. These Q_(u) values were measured at a temperature of67 K and input power of −10 dBm for lumped-element RF resonators havinga center frequency of about 1.85 GHz. The solid line at Ba/Dy=2represents the on-stoichiometric value of the 1:2:3 compound. It isagain observed that the highest Q values are obtained for compositionsthat deviate significantly from the on-stoichiometric ratio,particularly for Ba/Dy ratios between about 1.5-1.8, more particularlypeaking at between about the 1.6-1.7 ratio. FIG. 28 displays theunloaded quality factor (Q_(u)) as a function of the Ba/Dy ratio for thesame DBCO thin films of varying compositions measured at a temperatureof 77 K and input power of −10 dBm. While there is more scatter in thedata at this temperature which is nearer T_(c), the data still clearlyshow that the highest Q values are obtained for compositions thatdeviate significantly from the on-stoichiometric ratio, particularly forBa/Dy ratios between about 1.5-1.8, more particularly peaking around the1.6 ratio.

The Q values of (RE)BCO filters can degrade as a function of increasinginput power. The ability of (RE)BCO filters to maintain high Q values asa function of increasing input power is an important requirement forhigh performance filter systems. FIG. 29 displays the ratio of unloadedQ values at 67 K measured at high (+10 dBm) and low (−10 dBm) inputpowers for resonators made from DBCO film of different composition. Highvalues of Q_(+10dBm)/Q_(−10dBm) indicate better power handlingcapability and superior performance. It can be seen that increasinglyhigher ratios are obtained as the DBCO composition deviates further fromthe on-stoichiometric value (Ba/Dy=2), indicated by the solid verticalline. FIG. 30 plots the ratio of Q measured at high power to low powerat 77 K for several DBCO films of varying composition. This figure alsoshows that excellent power handling is obtained even for compositionsthat deviate substantially from the on-stoichiometric value.

The input power levels to the (RE)BCO filter also affects theirperformance by generating different amounts of intermodulationdistortion, as described below.

We further evaluated these materials by growing thin films on 2″ MgOsubstrates and patterning them into 10-pole filter circuits of a typesuitable for commercial cellular communications applications. FIG. 20shows a layout of the filter design. The filters were tuned, and theirperformance was evaluated in terms of insertion loss, return loss, andout-of-band rejection. In addition, we used these 10-pole filters tomeasure the nonlinear properties of these materials in terms of theirthird-order intermodulation distortion (IMD). A block diagram of thetest setup is shown in FIG. 21. For these measurements, tones of equalpower at two different closely-spaced frequencies f₁ and f₂ werecombined and applied to the filter at specific power levels. Thelocation of these input tones is in-band, far from the band edge, orclose to the band edge. The output power of the third-order mixingproduct at frequency 2f₁-f₂ is then measured in a spectrum analyzer. Themagnitude of the output signal from the filter at these frequencies isan important measure of the RF nonlinearities of the filter anddetermines its suitability for many microwave applications. The presenceof intermodulation distortion reflects the current density dependence ofthe surface reactance, X_(s), of the superconducting thin film (T. Dahm& D. J. Scalapino, J. Appl. Phys. 81 (4), pp 2002-2009) (1997). Incontrast, nonlinearity in the surface resistance, R_(s), of the thinfilm would be reflected in an increase in the insertion loss of thefilter. This type of nonlinearity is not generally a limiting factor inthe application of superconducting thin films to RF and microwavefilters.

We have utilized three IMD tests to assess the applicability of our HTSthin film materials for applications in RF/microwave filters.

-   -   1. In-band Test. Two-tone input signals are applied near the        center of the AMPS B Passband (835 MHz to 849 MHz). The input        frequencies are at f₁=841.985 MHz and f₂=842.015 MHz at power        levels of −20 dBm each. The intermodulation spurious product is        measured at 842.045 MHz. The intermodulation spurious product        power at this frequency measured at the output of the filter        must be <−105 dBm.    -   2. Near-Band Test. Equal amplitude input signals are applied at        851 MHz and 853 MHz, and the intermodulation spurious product        power level is measured at 849 MHz. The specification is the        minimum power level of input tones that produce intermodulation        spurious products in the AMPS B Passband with power levels of        −130 dBm at the output. This input power level must be >−28 dBm.    -   3. Out-of-Band Test. Equal amplitude input signals are applied        at 869.25 MHz and 894 MHz, and the intermodulation product is        measured at 844.5 MHz. The requirement is the minimum power        level of input tones to cause intermodulation products in the        AMPS B System Passband to reach −130 dBm at the output of the        filter. This input test signal power levels must be >−12 dBm.

We fabricated B-band cellular microwave filters from several (RE)BCOthin films which were grown by in situ reactive coevaporation onto 2″MgO substrates. Each double-sided wafer yields two filters, each havinga size of 18 mm×34 mm. The patterned (RE)BCO structures arequasi-elliptic 10-pole filters with 3 pairs of transmission zeros oneither side of the frequency passband. FIG. 22 shows the typicalresponse of such a filter. The positions of the frequencies for thetwo-tone IMD tests are shown.

FIG. 23 shows the IMD values measured at 79.5 K as a function of Ba/Dyratio for several 10-pole B-band filters patterned from optimized Dy-BCOfilms. Note that all the filters measured meet the requirements, whichare indicated by dotted lines. FIGS. 24 and 25 show the IMD values as afunction of the Ba/RE ratio measured at 79.5 K for several 10-poleB-band filters patterned from optimized Ho-BCO and Er-BCO films. FIG. 26shows the IMD values measured at 79.5 K for four 10-pole B-band filterspatterned from optimized Nd-BCO films.

Intermodulation distortion in HTS filters arises due to nonlinearity ofthe microwave surface reactance, X_(s), of the thin films. (R. B.Hammond et al, J. Appl. Phys. 84 (10) pp 5662-5667 (1998)). In general,at high microwave current densities in HTS thin films X_(s) ceases to beconstant and independent of current density, and begins to increase withincreasing current density. Commonly there is a maximum current density,J_(IMD), at which X_(s) retains its low current density value, and abovewhich X_(s) increases. In this paper by Hammond et al, the relationshipsbetween measured parameters and the material parameter J_(IMD) aredescribed. This relationship can be summarized as follows

$j_{IMD} = {\frac{Q_{L}^{2}}{\omega_{0}}\frac{1}{\Gamma_{IMD}}\sqrt{\frac{P_{IN}^{3}}{P_{OUT}}}}$

here Q_(L) is the loaded quality factor of the resonator, ω₀ is theresonant frequency, these two functions depend on the filter function tobe realized, Γ_(IMD) is a factor which depends only on the geometry ofthe resonator, and P_(IN) and P_(OUT) are the input and output powersfrom an intermodulation measurement.

The out-of-band IMD test requirement corresponds to a minimum J_(IMD) inthe HTS thin film of 1×10⁷ A/cm². The DBCO films surpass thespecification by 14 dB, which here corresponds to a factor of 5. Thus,the DBCO films have a J_(IMD) of 5×10⁷ A/cm². For filter applicationsJ_(IMD) in HTS thin films must be >1×10⁷ A/cm², more preferably >2×10⁷A/cm², and most preferably >3×10⁷ A/cm².

Methods of Manufacture

We have grown our (RE)BCO thin films using an in situ reactivecoevaporation (RCE) deposition technique which has been successfullyused to manufacture large-area YBCO HTS thin films. This is afabrication technique that readily lends itself to high volume filmproduction and manufacturability. The yield of high-performancemicrowave filters made from films grown by RCE is typically >90%. A keycomponent of this growth method is the use of a radiative heater thatinternally maintains an oxygen partial pressure that is greater than ˜10mTorr. The heater also incorporates a window that allows exposure of therotating substrates to high vacuum, where evaporation and deposition ofthe source materials occurs. Our substrates are typically MgO singlecrystals up to 2″ in diameter that are rotated continuously between thewindow and the oxidation pocket at 300 rpm. The chamber ambient pressureaway from the pocket is ˜10⁻⁵ Torr. This configuration providessufficient oxygen pressure for stability of the high-T_(c) phase whilethe metallic evaporation sources are simultaneously free from oxidation,and the evaporated species are free from scattering. The rare earthelements Er, Ho, and Dy are evaporated from electron beam sources, Ndand Cu are evaporated from either electron beam sources or resistivesources, and Ba is evaporated from a thermal furnace or a resistivesource. The typical deposition rate is ˜2.5 Å/sec. The depositiontemperature for the films discussed here is 760 to 790° C., and the filmthickness is about 700 nm. The films were deposited directly onto MgOsubstrates, with the exception of Nd-BCO, which presently requires athin buffer layer in order to achieve the best results.

Unlike yttrium, which melts readily, some rare earth elements such asEr, Ho, and Dy sublime during e-beam evaporation, thereby makingcompositional control more challenging. We routinely use quartz crystalmonitors (QCM) as our primary rate controllers. However, the sublimingmaterials are never molten at our evaporation rates; rather, theelectron beam digs a hole in the metallic source material so that theplume shape changes significantly during the course of the depositionrun. Therefore, the QCMs are not able to correctly monitor the changingamount of RE vapor flux. To alleviate this difficulty we have employedhollow-cathode-lamp (HCL) atomic absorption (AA) evaporation fluxsensors to monitor and control these subliming materials. Since the AAlight beam passes through the entire plume of evaporated species, thistechnique can more accurately monitor the amount of evaporated flux.

The oxygen pocket pressure and deposition rate used to achieve optimalresults are similar for the (RE)BCO films that we have studied. We havefound that the best substrate temperatures for Er, Ho, Dy, and Nd are780, 790, 790, and 780° C., respectively. These temperatures aresignificantly higher than the temperature of 760° C. we use to achieveoptimal RF properties for YBCO. The use of different growth conditionsfor the (RE)BCO materials compared to YBCO is mandatory in order toachieve the very best RF properties. For example, higher growthtemperatures for the (RE)BCO materials as compared to YBCO are generallyrequired in order to insure the absence of deleterious misalignedgrains. The composition must also be optimized for this purpose, as wehave discussed. In general, many aspects of film growth affect thedefect structure in (RE)BCO thin films, and thus RF properties,including a) growth temperature, b) growth rate, c) oxygen pressure, andd) stoichiometry. Specific choices for (a). (b), and (c) may yielddifferent optimized properties and different optimized compositions.

Although the foregoing invention has been described in some detail byway of illustration and example for purposes of clarity andunderstanding, it may be readily apparent to those of ordinary skill inthe art in light of the teachings of this invention that certain changesand modifications may be made thereto without departing from the spiritor scope of the appended claims.

We claim:
 1. A superconducting article comprising: substrate, at leastone buffer layer supported by the substrate, and a thin film disposed onthe substrate having the nominal composition of RE_(z)Ba_(y)Cu₃O_(x)wherein RE is a rare earth, wherein the ratio of y/z is 1.65±10% and xis between 6 and 7 inclusive, and the article including 45-degree grainboundaries in a concentration of <1%.
 2. The article of claim 1 whereinthe thin film is deposited on the substrate by reactive coevaporation.3. The article of claim 1 wherein the thin film has a superconductingtransition temperature >87K.
 4. The article of claim 1 wherein thesubstrate is lattice matched to the thin film.
 5. The article of claim 1having an RMS surface roughness of less than about 10 nm.
 6. The articleof claim 1 wherein the topmost buffer layer is lattice matched to thethin film.
 7. The article of claim 6 wherein one of the buffer layers isMgO.
 8. The article of claim 6 wherein one of the buffer layers isAl₂O₃.
 9. The article of claim 1 wherein the substrate is rigid.
 10. Thearticle of claim 1 wherein the substrate is a single crystal.
 11. Thearticle of claim 1 wherein the substrate is selected from the group MgO,Al₂O₃, LaAlO₃, NdGaO₃, (La_(0.18)Sr_(0.82))(Al_(0.59)Ta_(0.41))O₃, andSrTiO₃.
 12. The article of claim 1 wherein the substrate has a thermalexpansion match to the thin film.
 13. The article of claim 1 wherein thesubstrate has a surface area >3 square inches.
 14. The article of claim1 containing a-axis-oriented grains in a concentration of <1% relativeto c-axis-oriented grains.
 15. A superconducting article comprising: asubstrate, and a thin film disposed on the substrate having the nominalcomposition of RE_(z)Ba_(y)Cu₃O_(x) wherein RE is a rare earth, whereinthe ratio of y/z is 1.65±10% and x is between 6 and 7 inclusive, andwherein the thin film deposited by reactive coevaporation.
 16. Asuperconducting article comprising: a rigid substrate, and a thin filmdisposed on the substrate having the nominal composition ofRE_(z)Ba_(y)Cu₃O_(x) wherein RE is a rare earth, wherein the ratio ofy/z is 1.65±10% and x is between 6 and 7 inclusive, and the articleincluding 45-degree grain boundaries in a concentration of <1%.
 17. Thearticle of claim 17 wherein the thin film is deposited on the substrateby reactive coevaporation.
 18. The article of claim 17 wherein the thinfilm has a superconducting transition temperature >87K.
 19. The articleof claim 17 wherein the substrate is lattice matched to the thin film.20. The article of claim 17 wherein the substrate has a thermalexpansion match to the thin film.